The present invention relates to the bicyclic phosphite of pentaerythritol monobromohydrin and processes for producing same, and additionally, it relates to the corresponding bicyclic phosphate and to a new family of polyphosphonates produced therefrom, and process for making and using same.
Certain bicyclic esters of phosphorous acid (Formula I) and of phosphoric acid (Formula II) having the bicyclo [2.2.2] octane structure are known: ##STR2##
The first phosphites and phosphates of types I and II (with Z being CH.sub.3, C.sub.2 H.sub.5, higher alkyls, or HOCH.sub.2) seem to have been prepared initially by chemists at Hooker Chemical Corporation (British Pat. No. 889,338, published Feb. 14, 1962, claiming a U.S. priority date of July 21, 1958), but the first publication relating to these compounds was J. G. Verkade and L. T. Reynolds, J. Org. Chem. 25, 663 (1960) with the synthesis of phosphite (I) with Z being CH.sub.3.
Other similar phosphites where Z was C.sub.2 H.sub.5, HOCH.sub.2, CH.sub.3 COOCH.sub.2, CH.sub.2 .dbd.CH(CH.sub.3)COOCH.sub.2, and CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5)COOCH.sub.2 were prepared by O. Neunhoffer and W. Maiwald, Chem. Ber. 95, 108 (1962) and by W. S. Wadsworth, Jr. and W. D. Emmons, J.A.C.S. 84, 610 (1962). The latter workers also described phosphates (II) where Z was C.sub.2 H.sub.5 and CH.sub.2 .dbd.CH(CH.sub.3)COOCH.sub.2.
Phosphite (I) and the corresponding phosphate (II) with Z being H have only been prepared more recently by E. J. Boros et al, J.A.C.S. 88, 1140 (1966).
Phosphate (II) with Z being NO.sub.2 was prepared in 1926 by F. Zetzsche and E. Zurbrugg, Helv. Chim. Acta 9, 298 (1926). Its synthesis was repeated by W. H. Chang, J. Org. Chem. 29, 3711 (1964), and he at the same time also showed phosphates (II) with Z as C.sub.6 H.sub.5 and C.sub.6 Cl.sub.5 --OCH.sub.2. Last, G. Kamai and E. T. Mukmenev, Zh. Obschei Khim., 33, 3197 (1963) have reported the preparation of a diphosphite corresponding to Formula (I) where Z is (C.sub.2 H.sub.5 O).sub.2 POCH.sub.2.